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3.1 INTRODUCTION:
If one were to list the major technological developments that have added to the
comforts of living, glass lenses as an aid to failing vision, glass windows to bring day
light into houses structures while providing protection from the harsh elements of nature,
glass in the light bulb to provide a similar function after dark and glass fibers for
For the glass window and the glass bulb to function, the optical transmission
property is important. The correction for the failing vision and glass fiber communication
is based upon the refractive, optical dispersion and transmission properties of glass.
Beside these, there are many more technological advances where the optical properties of
glass play a pivotal role [19]. The most obvious optical property of ordinary silicate
Valuable information about the structure of glasses can be obtained from their
spectra and in molecules the rotation and vibration cause the electrons to form band
spectra where as in solid amorphous materials like glasses. The optical transitions are
3.2.1 ABSORPTION:
in a medium. The nature of this process depends on the frequency of the radiation and on
The most direct and perhaps simplest method for probing the band structure of
relative rate of decrease in light intensity along its propagation path. The
absorption edge, provides a standard method for the investigation of optically induced
electronic transitions and give some idea about the band structure and energy gaps in both
Basically two types of optical transitions can occur at the fundamental edge i.e.
direct and indirect optical transitions. In direct optical transition the wave vector of
electron remains unchanged. However the wave vector must change in indirect transition.
The fundamental absorption edge in the most disordered materials usually follows the
the width of tail of localized states in the band gap of the amorphous materials,
E = Ec - Ea
Mott and Davis [25] suggested the following expression for the optical transitions
Where n = 1/2 or 3/2 for direct transition depending on whether the transition is
In non-crystalline materials absorption can arise from the inter band transitions
involving the tails of the localized states. The absorption in many amorphous materials is
suggested to be associated with indirect transitions, which obey the above eq. [26].
corresponds to the high energy spectrum region is dominant. The absorption coefficient
() rises very sharply at a spectral region called the absorption edge. The corresponding
photon energy for this absorption edge provides the optical gap of the material.
It is an important [27] assumption that the mobility gap is equal to twice the
ABSORPTION]:
The transition between the states within a single band is known as intra band
transition. When a free electron (or a hole) absorbs a photon it excited to another state in
the same band, this type of absorption is known as the intra band absorption.
3.2.1.3. ABSORPTION
It is the absorption on the low energy side of the fundamental absorption edge and
is associated with the transitions from or to impurity or defect levels in the gap. Another
absorption process in amorphous materials is also observed at very low frequencies due
give rise to absorption. In amorphous material the lattice absorption process are retained
to a degree, which depends on the materials, but the fine structure presents in the
3.2.2 TRANSMITTANCE:
frequency change the nature of this process depend on the frequency of the radiation and
incident light or other electromagnetic radiation, equal to the ratio of the flux. The
transmittance depends on the path length of the radiation and on its wave length [28].
radiatons depends not only upon the absorbed but also on the amount of reflected
radiation at the interfaces. It is also possible that diffused transmission may occur, that is
transmission in which the laws of refraction are not obeyed on the microscopic scale and
part of the radiation is scattered and lost form the beam without being absorbed.
measurements made. They may be made easily, conveniently and with moderately good
3.2.3 REFLECTANCE:
The process in which the incident radiation on the surface of the material bounces
back into the original medium without any change in its frequency rather than passing
into the second medium is called reflection [22]. Reflection depends upon the frequency
The reflectance is defined as the ratio of reflected luminous flux to the incident
flux.
R+A+T=1 (3.3)
R = Reflectance.
A = Absorbance.
T = Transmittance.
3.3.1 DENSITY:
material in a unit volume and is usually an additive property. However, the structure
developed after the reaction of constituents determines the value of density in a system
such as glass. The calculation of density are therefore, based on assumptions about the
structure of glass. The structure of glass is determined by the interatomic for ces between
glass forming contains (like Ge+2 , B+3, Si+4, P+5) and surrounding oxygen anions.
In pure silica glasses, each oxygen bridges two silicon while other silicate glasses
contains both bridging and non-bridging oxygen atoms. The ratio of bridging to non-
changes in the density of glass. These changes may be due to the differences in densities
Parameters determined from density are oxygen packing density and molar
The molar volume of binary and ternary phosphate glasses have been estimated
by the relation,
Where,
Molar volume is an important parameter which can be used to explain the density,
modulus of rigidity, coefficient of thermal expansion and transition temperature data. [51,
52, 53],
The oxygen packing density was calculated by using the following expression as
oxygen atoms in the composition and the density of the glass sample.
glass. [31].
4.1 REVIEW ON OPTICAL PROPERTIES OF
PHOSPHATE GLASSES
In recent years the optical band gap of some binary and ternary phosphate glasses
has been studied [58-61]. A large amount of experimental data on the optical properties of
Austin and Garbet [40] describe that the absorption coefficient shows an
exponential behaviour in vanadium phosphate glasses with Ni, Co, Cu, ions but tails in
the absorption have been reported by Nunoshita et. A1 [41] Hogarth and Gharuri [42]
also reported similar results on cadmium phosphate and cadmium-zinc phosphate glasses.
These tails were suspected to be due to the presence of impurities, structural defects or
other kind of in homogeneity. It is accepted that in most cases the d.c photoconduction
measurements follow the optical absorption gap, which in some cases yield mobility gap
Hogarth and Hosseni [24], Khawaja etal. [73], Kutub et.al. [74], and Siddiqi
et.al [75] studied the absorption edges of some binary and ternary phosphate glasses
having colorant centers i.e transition element oxides that have been used as modifiers.
The fundamental absorption edges [43] of the vanadium phosphate and vanadium-
Tellurium phosphate glasses in the short wave length part of the visible region are
measured by Hogarth and Hosseini. It was found that the fundamental absorption of
these glasses is dependent on composition and arises from direct forbidden transition and
occurs at photon energy in the range 1.9--2.6ev depending upon the composition. They
concluded that the carrier concentration in the localized levels ( band tails) depends upon
the total number of available sites which in the case of vanadium-phosphate glasses are
In their research publication [43] they suggested that in transition metal oxide
glasses a photon with a certain energy range could be absorbed by transition metal ions
ii. The absorption may be due to the internal transition between the d-shell
electrons.
that optical absorption may be attributed to the change in the ratio of concentration of Cu +
and Cu++ ions in the glasses as a consequence of changing the sodium content. Siddiqi et.
al. [76,75]. Studied the optical properties of manganese phosphate and cadmium
manganese phosphate glasses. They observed that, at zero field, band gaps were
band gap decreases with the increase of applied field in binary MnO-P 2O5 glasses but in
ternary MnO-CdO-P2O5 glasses the deduced values of band gaps were found to be almost
absorption tail of vanadium phosphate glasses in the range 3850-3000 cm-1. The band
reduced V+4 ions was concluded to be largely responsible for the variation of E g and of
The Band gap in cadmiun zinc phosphate glasses by absorption and photo
conduction measurements was determined by Ghauri et. al [45]. The two values of the
band gaps are nearly same within the experimental error. The photoconduction band gap
shows a slow decrease with an increase in the applied field. The results have been
Tauc [46] believes that the variation of absorption coefficient with photon energy
is due to the electronic transition between the localized states. Where as, Mott and Daivs
[35] were uncertain about the explanation because the slopes of the observed exponential
behaviour do not change for a great variety of materials. Redfied and Afromawitaz [62]
suggested that this region of absorption edge is related to imperfection in the material.
While Vasilyev et. al [47] suggested that the spectral dependence can be related to a
reported that the optical absorption is due to forbidden indirect transition. They reported
the basic measurements on the cadmium-zinc phosphate glass and made some
phosphate glasses has been measured in the UV-visible spectral region by photo
absorption method.
Hogarth and Ghauri [63], Ghauri et al. [64], Nazar & Ghauri [65], Ahmad &
Hogarth [66] and Hikmat Shoar et al [67] had suggested that optical absorption in these
glasses were due to indirect electronic transition. It was found that optical band gaps of
these glasses were composition dependent, which is known as zero field optical band gap.
Ghuari et al [68] had also verified that non-crystalline materials like semi
Nadeem et al. [69], Bilal et al. [70], Chaudhry et al [71,72] had studied the
optical absorption spectra of some binary cadmium phosphate, zinc phosphate and
ternary cadmium-zinc phosphate glasses. It was found that absorption edges lie in the
UV- region of the spectra and optical band gaps of these glasses were.
4.2 PURPOSE OF THE PRESENT WORK:
There are many technical and biological applications of Phosphate glasses. The
phosphate glasses can be used as semiconductor and dielectrics. Due to the potential
application for transmission and detection of optical data and also in laser technology, the
phosphate glasses containing high concentration of rare earth ions are of interest.
Phosphate glass containers are used to store radioactive waste material. From the
Biological aspect phosphate glass ceramics are used for artificial bones. Thin Films of
The Purpose of the present review on optical properties of phosphate glasses was
to make an assessment of the kind of work which can be carried out with various
For the present work, Binary and Ternary systems of some phosphate glasses were
60%ZnO+40%P2O5
50%ZnO+50%P2O5
40%ZnO+60%P2O5
30%ZnO+70%P2O5
10%B2O3+30%ZnO+60%P205
20%B2O3+30%ZnO+50P2O5
30%B2O3+30%ZnO+40%P2O5
40%B2O3+30%ZnO+30%P2O5
has been carried out so far. We studied the binary systems of zinc phosphate glasses in
order to make a comparison with already published data [82] and also with ternary
For the preparation of all these binary and ternary phosphate glasses the relevant
amounts of the constituents were calculated for 10 gm samples, using the molecular
weight formula of required glass system. After weighing required amounts for each
composition, they were thoroughly mixed and then put in a platinum crucible. Which was
then kept in an electrically pre-heated furnace at 300C0 for half an hour to avoid the
fuming effect of P2O5. The crucible was then kept in electrically pre-heated furnace at
500C0 for further half an hour .Then it was at 1350C 0 for two or one hour to homogenized
melt. The molten form of the materials then casted in stainless steal discs of diameter 20
mm each.
Then samples were annealed at 200C for an hour to remove the mechanical and
After annealing, the discs shaped glass samples of binary and ternary systems
have been polished by grinding them on Silicon Carbide paper of different grades. For
Fine polishing the silicon carbide papers of grades 320 to 1000 were used. To achieve the
best optical transparency the samples were finally polished on micron grade polishing
paper.
The optical absorption and transmittance for all samples of glass were obtained in
measurements were done in wavelength scanning mode under the following parametric
conditions.
1. At room temperature
3. Reference is air.
illustrated in fig-5.1.
Figure 5.1
The density was measured by using Pyknometric Method. For this purpose
sartorious balance was used. In this method, at first a gravity bottle is weighed, then
gravity bottle with sample is weighed, then gravity bottle with toluene is weighed, finally
the gravity bottle with toluene and with sample is weighed. Then density is calculated by
- mass of sample * d
where,
prepared by using the melt-quench method under the same parametric conditions. The
density and optical band gap are the main concern of this study. The results related to
6.1 DENSITY
For various composition of binary and ternary glasses the results of the
measurements of density are listed in tables [3,4] .The same results related to these
glasses has been plotted with ZnO concentration in Fig.-6.1. From the graph it can be
seen that the variations of density is such that it decreases with decreasing amount of
In these binary glasses P2O5 is replaced by an equal amount of ZnO which may
cause the decrease of density with decrease of ZnO as shown in Fig -6.1.
At 60% ZnO white spots in glass has been observed .which are related to the
imperfectness of the glass and caused by the unavailability of the temperature due to
furnace limitations.
We know that the density of B2O3 is 1.84 gm/cm3 It is observed that the density of
6
Table 3:
during glass preparation. B2O3 is the glass former with highest bond strength. When we
are replacing P2O5 with B2O3 i.e low bond with high bond strength material may contract
the structure of the material which may cause the decrease in molar volume of glass and
The optical property such as the absorbency was measured by using the Hitachi
For various composition of binary and ternary phosphate glasses, the optical
absorption edge, which may refer the characteristic to the glassy state. The absorption
values for different wavelengths for different glass composition are calculated from these
= 2.303 A/D
Which has been derived from Lambard Beer's law|54|.
I = Io e-d
I / Io = e -d
Io / I = ed
log Io / I = log ed
A = d loge
A = d 0.4343
= A / 0.4343d
= 2.303A/d
Where,
d = thickness of the sample. Theoretical formula for given by Mott and Davis is
() = A (h - Eopt)2 / h
() h = A (h - Eopt)2
Where,
For various binary and ternary glass compositions, the observed data related to
above equation are given in Tables [5-12]. These data are plotted to determine the optical
band gap of these samples. The straight portion of these graphs shown in Fig- 6.2.9 to
Fig- 6.2.16.were extrapolated to meet x-axis at zero values of (h) 1/2. The values of
h at that point yield a direct measure of optical band gap energy. The values of
optical band gap for different composition of ZnO-P2O5 are lies 2.7-3.35eV while the
values of optical band gap for different composition of B2O3-ZnO-P2O5 lie between 2.4-
The results of measurement of optical band gap are listed in Table [13-14] .For
binary phosphate glasses (ZnO-P2O5) the optical band gap data has been depicted in Fig-
6.2.17, as a function of ZnO composition expressed in mole percent. It can be seen that
variation of optical band gap is such that at first it increases, then decreases and again
increases with decreasing amount of ZnO in binary ZnO-P2O5 glasses. This may be due
to the fact that ZnO acts both as a modifier and as an intermediate. At low values of ZnO
If it does not enter into the glass forming network and only acts as an impurity or
structural defect it causes the band tailing and have reduces the band gap energy.
However if it does enter into the network, it increases the band gap as described in fig-
6.2.17 [55],
At 60% ZnO white spots in glass has been observed , which are related to the
imperfectness of the glass and caused by the unavailability of the temperature due to
furnace limitation, which may cause to decrease in the optical band gap.
In the ternary phosphate glasses (B2O3-ZnO-P2O5) the optical band gap data has
The variation of band gap is such that at first it increases with increases amount of
B2O3 and then it decrease with increasing amount of B2O3 keeping the amount of ZnO
constant as shown in figure [6.2.18]. This may be due to certain structural change
= 2.303A hw = hc /
A (hw)1/2
(nm) (cm-1) d (ev)